Catalyst for the demetalation of a hydrocarbon charge stock

ABSTRACT

This specification discloses the demetalation of a hydrocarbon charge stock and a catalyst for the demetalation. The catalyst comprises a manganese nodule which has been subjected to a treatment to improve its catalytic activity for demetalation. The treatment involves removal of at least a portion of the manganese dioxide component of the manganese nodule selectively with respect to the iron oxide component of the nodule. Demetalation of the hydrocarbon charge stock is effected by contacting the charge stock with hydrogen in the presence of the catalyst.

ite Huang et a1.

a atet [191 11 3,772,11 [451 Nov. 13, 1973 A. Nam, Trenton, both of N.J.; Anthony J. Silvestri, Morriville, Pa.

[21] Appl. No.: 165,353

[52] US. Cl. 208/251 H, 208/253 [51] lnt. Cl ..C10g 17/00, ClOg 19/00 [58] Field of Search 208/251, 253

[56] References Cited UNITED STATES PATENTS 11/1933 Jenness 23/234 l/1957 Powell 196/40 Rolf 75/103 Miale 208/110 Primary ExaminerDelbert E. Gantz Assistant Examiner-Juanita M. Nelson Attorney-Frederick E. Dumoulin et al.

[57] ABSTRACT This specification discloses the demetalation of a hydrocarbon charge stock and a catalyst for the demetalation. The catalyst comprises a manganese nodule which has been subjected to a treatment to improve its catalytic activity for demetalation. The treatment involves removal of at least a portion of the manganese dioxide component of the manganese nodule selectively with respect to the iron oxide component of the nodule. Demetalation of the hydrocarbon charge stock is effected by contacting the charge stock with hydrogen in the presence of the catalyst.

15 Claims, N0 Drawings CATALYST FOR THE DEMETALATKON OF A HYDROCARBON CHARGE STOCK BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to the treatment, and a catalyst therefor, of a hydrocarbon charge stock to effect removal therefrom of metal compounds.

2. Description of the Prior Art US. Pat. application Ser. No. 100,931, filed Dec. 23, 1970, discloses a procedure for the treatment of a hydrocarbon charge stock to effect the removal therefrom of metal compounds by contacting the hydrocarbon charge stock with hydrogen in the presence of, as a catalyst, a manganese nodule. This application also discloses that the manganese nodule, prior to use as the catalyst, may be subjected to a pretreatment. Pretreatments to which the manganese nodule may be subjected include sulfiding. They also include leaching to remove therefrom one or more components of the nodule. Leaching, as disclosed in this prior application, effects the removal from the nodules of copper, nickel, or molybdenum, or any two, or all three, of these metals. Leaching of copper and nickel is effected by treating the manganese nodules with an aqueous solution of a strong acid such as hydrochloric, sulfuric, or nitric acid. Leaching of molybdenum is effected by treating the manganese nodules with an aqueous solution of sodium hydroxide or sodium carbonate.

US. Pat. No. 3,509,041 discloses the use of manganese nodules, after pretreatment by base exchange to bond hydrogen ions thereto, in hydrocarbon conversion reactions, specifically cracking, hydrocracking, oxidation, olefin hydrogenation, and olefin isomerization.

US. Pat. No. 3,471,285 discloses the selective recovery of manganese and iron from'manganese nodules which also contain cobalt and nickel by reducing the nodules at elevated temperatures and then leaching with an aqueous solutionof ammonium sulfate.

U.S. Pat. No. 2,103,219 also discloses the procedure disclosed in US. Pat. No. 1,937,488.

U.S. Pat. No. 1,937,488 discloses the treatment of a manganese ore such as pyrolusite with a reducing agent such as methanol or hydrogen to-convert the manganese dioxide component of the ore to manganous manganite, i.e. manganese sesquioxide, and then subjecting the ore to treatment with an aqueous solution of an acid such as nitric acid or sulfuric acid to leach the manganous oxide portion of the manganous manganite from the ore. The procedure is stated to improve the catalytic activity of the ore for such reactions as oxidation of carbon monoxide and synthesis of methanol.

SUMMARY OF THE INVENTION In accordance with the invention, the catalytic activity of a manganese nodule for the demetalation of ahydrocarbon charge stock containing metals is improved by removing at least a portion of the manganese dioxide component of the nodule selectively with respect to the iron oxide component of the nodule. The manganese nodule, subsequently, is employed as a catalyst for the demetalation of a hydrocarbon charge stock containing metals.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Various hydrocarbon charge stocks such as crude petroleum oils, topped crudes, heavy vacuum gas oils, shale oils, oils from tar sands, and other heavy hydrocarbon fractions such as residual fractions and distillates, contain varying amounts of non-metallic and metallic impurities. The non-metallic impurities include nitrogen, sulfur, and oxygen and these exist in the form of various compounds and are often in relatively large quantities. The most common metallic impurities include iron, nickel, and vanadium. However, other metallic impurities, including copper, zinc, and sodium, are often found in various hydrocarbon charge stocks and in widely varying amounts. The metallic impurities may occur in several different forms as metal oxides or sulfides which are easily removed by simple processing techniques such as by filtration or by water washing. However, the metal contaminants also occur in the form of relatively thermally stable organo-metallic complexes such as metal porphyrins and derivatives thereof along with complexes which are not completely identifiable and which are not so readily removed.

The presence of the metallic impurities in the hydrocarbon charge stocks is a source of difficulty in the processing of the charge stocks. The processing of the charge stock, whether the process is desulfurizing, cracking, reforming, isomerizing, or otherwise, is usually carried out in the presence of a catalyst and the metallic impurities tend to foul and inactivate the catalyst to an extent that may not be reversible. Fouling and inactivation of the catalyst are particularly undesirable where the catalyst is relatively expensive, as, for example, where the active component of the catalyst is platinum. Regardless of the cost of the catalyst, fouling and inactivation add to the cost of the processing of the charge stock and therefore are desirably minimized.

Demetalation has been effected by catalytic hydroprocessing of the charge stock. However, catalytic hydroprocessing, similar to other processing of the charge stock, results in the catalyst becoming fouled and inactivated by deposition of the metals on the catalyst. There is no convenient way of regenerating the catalyst and it ultimately must be discarded. Since the catalysts heretofore employed are relatively expensive, catalytic hydroprocessing to demetalize hydrocarbon charge stocks has suffered from adverse economics.

By employing a catalyst obtained from manganese nodules, an economical and effective demetalation of a hydrocarbon charge stock is obtained. Manganese nodules are readily available in large quantities and are relatively inexpensive. Thus, whereas the catalyst derived from manganese nodules becomes fouled and inactivated by the demetalizing process, the manganese nodules are obtainable at such low cost that the fouled and inactivated catalyst can be discarded without significant effect on the economics of the demetalizing process.

Manganese nodules, as is known, are naturally occurring deposits of manganese dioxide (MnO found on the floor of bodies of water. They are found in abundance on the floors of oceans and lakes. For example, they are found in abundance on the floor of the Atlantic and Pacific Oceans and on the floor of Lake Michigan. The nodules are characterized by a large surface area,i.e.,in excess of square meters per gram. The

nodules have a wide variety of shapes but most often those from the oceans look like potatoes. Those from the floor of bodies of fresh water, such as the floor of Lake Michigan, tend to be smaller in size. Their colors vary from earthy black to brown, depending upon their relative manganese and iron content. The nodules are porous and light, having an average specific gravity of about 2.4. Generally, they range from one-eighth inch to 9 inches in diameter but may extend to considerably larger sizes approximating 4 feet in length and 3 feet in diameter and weighing as much as 1,700 pounds. The nodules also contain iron oxide, i.e., ferric oxide (Fe O Additionally, the nodules contain oxides of silicon and aluminum, carbonates of calcium and magnesium, the sulfate and phosphate of calcium, and small amounts of the oxides of molybdenum, zinc, lead, vanadium, and rare earth metals. The proportions of the various components of the nodules vary. The maximum, minimum, and average assay of 30 examples of manganese nodules from the worlds oceans are shown below:

Weight Percentages In the process of the invention, at least a portion of the manganese dioxide component of the manganese nodule is removed selectively with respect to the iron oxide component of the nodule. Stated otherwise, the iron oxide component is not removed to any appreciable extent from the manganese nodule. By this process, a catalyst is obtained which has an activity for demetalation of a hydrocarbon charge stock greater than that of the manganese nodule from which the catalyst was obtained. The catalyst also has an activity for desulfurization of the hydrocarbon charge stock greater than that of the manganese nodule from which the catalyst was obtained.

Selective removal of the manganese dioxide component of the manganese nodule with respect to the iron oxide component may be carried out employing any suitable procedure. An effective procedure for this purpose involves conversion of the manganese dioxide component to a compound which is soluble in a solvent in which the iron oxide component of the manganese nodule, or any derivative of the iron oxide component formed concomitantly with conversion of the manganese dioxide component, is substantially insoluble. The procedure also involves leaching the manganese nodule with the solvent in which the compound to which the manganese dioxide component has been converted is soluble and in which the iron oxide component, or any derivative of the iron oxide component formed concomitantly therewith, is substantially insoluble, to dissolve and remove from the manganese nodule at least a portion of this compound. Preferably, the manganese nodule is subjected to treatment, as by contact with a reagent capable of reducing the manganese of the manganese dioxide component to a lower valent state and to treatment, as by leaching with an aqueous solvent,

to dissolve and remove the compound containing the manganese in the lower valent state.

As stated, the manganese dioxide component of the manganese nodule is removed selectively with respect to the iron oxide component. By reducing the manganese of the manganese dioxide component to a lower valent state, a manganese compound is formed which is soluble in various aqueous solvents in which the iron oxide component of the manganese nodule is substantially insoluble. Further, the manganese compound wherein the manganese is of lower valent state is soluble in various aqueous solvents in which any derivative of the iron oxide component formed concomitantly with reduction of the manganese is substantially insoluble. Thus, an aqueous solvent may be selected in which the manganese compound containing the manganese in lower valent state is soluble selectively to the iron oxide or any concomitantly formed derivative of the iron oxide.

Various procedures and reagents may be employed for reducing the manganese of the manganese dioxide component to a lower valent state and for dissolving and removing the manganese compound containing the manganese in the lower valent state. For example, the manganese nodule may be contacted with carbon monoxide. The manganese in the manganese dioxide component of the manganese nodule has a valence of 4. It is capable of existing in the lower valent states of 2 and 3. Most commonly, of the lower valent states, it exists in the divalent state. By treatment of the manganese nodule with carbon monoxide, the carbon monoxide reacts with the manganese dioxide wherein the manganese has a valence of 4 to form manganous oxide wherein the manganese has a valence of 2. Simultaneously, the carbon monoxide, wherein the carbon has a valence of 2, is oxidized to carbon dioxide, wherein the carbon has a valence of 4. The manganese nodule can then be leached with an alkaline aqueous solution. For example, the manganese nodule may be leached with an aqueous solution of ammonium hydroxide and ammonium carbonate. Ammonium carbamate is the reaction product of ammonium hydroxide and ammonium carbonate. The manganous oxide forms a soluble complex with the'ammonium carbamate but the iron oxide component of the nodule, or any reaction product of the iron oxide component with the carbon monoxide, is substantially insoluble in the solution.

Another procedure for reducing the manganese dioxide component of the manganese nodule involves contacting the manganese nodule with sodium chloride dissolved in an aqueous acid medium. In the acid medium, the sodium chloride reacts with the manganese dioxide to form manganous chloride wherein the manganese has a valence of 2 and the chloride of the sodium chloride is oxidized to form zero valent chlorine. On the other hand, the sodium chloride does not react with the iron oxide component to form ferric chloride. However, iron oxide is soluble in acid media where the pH is not greater than 3. Thus, in this procedure, in order to avoid solution of the iron oxide, the acid medium must have a pH greater than 3. A separate step of leaching the manganese nodules to dissolve and remove the manganous chloride is not necessary in this procedure since the step of converting the manganese dioxide to manganous chloride in the aqueous acid medium also dissolves and removes manganous chloride.

Still another procedure for reducing the manganese dioxide component of the manganese nodule involves contacting the manganese nodule with sulfur dioxide. Sulfur dioxide reacts with manganese dioxide to form manganous sulfate and sulfite. The sulfur of the sulfur dioxide is oxidized to sulfate and sulfite. The sulfur dioxide, however, does not react with the iron oxide component of the nodule. The manganese nodule can then be leached with water to dissolve and remove the manganOuS sulfate and sulfite.

Treatment of the manganesenodule to remove selectively the manganese dioxide component should be carried out to remove a significant portion of the manganese dioxide component. By significant portion" is meant a portion which, when removed from the manganese nodule, will result in an improvement in the catalytic activity of the manganese nodule for demetalation. The removal of any amount of the manganese dioxide component 'will result in an improvement in the catalytic activity of the manganese nodule. Preferably, however, this portion is at least 25 percent by weight of the manganese dioxide component. It may be all of the manganese dioxide component. However, removal of all of the manganese dioxide component is ordinarily impractical. Accordingly, this portion will usually not be greater than 95 percent by' weight of the manganese dioxide component.

As stated, removal of at least a portion of the manganese dioxide component is selective with respect to the iron oxide component. However, treatment of the manganese nodule to remove the manganese dioxide component may unavoidably remove a portion of theiron oxide component. Removal of a small portion of the ironoxide component concomitantly with the manganese dioxide component will not have an appreciable effect on the catalytic activity of the manganese nodules for demetalation. However, the amount of iron oxide removed should not be greater than percent of the amount of manganese dioxide removed. Thus if the amount of manganese dioxide removed is 25 percent by weight of the manganese dioxide, the amount of iron oxide removed should not be greater than about 2.5 percent by weight of the iron oxide component.

The treatment to remove selectively at least a portion of the manganese dioxide component of the nodule may be carried out on the manganese nodule substantially as mined, or recovered, from the floor of the body of water in which it occurred. Thus, the nodule, as

treatment of sulfiding prior to use for demetalation.

Sulfiding of the manganese nodule increases the catalytic activity of the nodule for demetalation of the charge stock to an extent in addition to the increase resulting from the removal of at least a portion of the manganese dioxide component. The sulfiding can also increase the extent of desulfurization of the hydrocarbon charge stock. This treatment is carried out by subjecting the nodule, subsequently to removing at least a portion of manganese dioxide component, to the action of hydrogensulfide. The hydrogen sulfide may be pure or may be mixed with other gases. However, the hydrogen sulfide should be substantially free of oxygen. The temperature of sulfiding may be from about 300 F. to about 450 F. and the time of sulfiding may be from about 4 to about 8 hours. The sulfiding may be effected, for example, by passing the hydrogen sulfide over the manganese nodule continuously during the sulfiding reaction. The space velocity of the hydrogen sulfide is not critical and any space velocity compatible with the equipment and such that some hydrogen sulfide is continuously detected in the exit stream is suitable.

The nodule, prior to use as a catalyst for demetalation, may be crushed and sized to obtain a desirable particle size depending upon the type of demetalation operation employed, for example, a fixed bed operation, an ebullition operation, or otherwise.

The demetalation reaction is carried out by contacting the hydrocarbon charge stock simultaneously with manganese nodule and with hydrogen. The temperatures at which the reaction is carried out can be from about 650 F. to about 850 F. At higher temperatures, a greater degree of demetalation occurs. However, the temperatures employed should not be so high as to effect an undesirable degree of alteration of the charge stock. Preferably, the temperatures employed are in the range of 750-850 F. The pressures at which the reaction is carried out can be from about to 3,000 pounds per square inch gauge (psig). Preferably, the pressures employed are in the range of 500-2,000 psig. Where the reaction is carried out by passing the hydrocarbon charge stock through a bed of the manganese nodule, the liquid hourly space velocity (LHSV) of the charge stock can be from about 0.2 to 4, preferably 0.5 to 2, volumes of charge stock per volume of manganese nodule per hour. Hydrogen circulation is at rates of 2,00015,000, preferably 5,000l0,000 standard cubic feet of hydrogen per barrel of hydrocarbon charge stock. The hydrocarbon charge stock along with the hydrogen may be passed upwardly through a fixed bed of manganese nodule in an upflow reactor or may be passed downwardly through a'fixed bed of manganese nodule in a downflow trickle-bed reactor. The reaction may also be carried out by passing the charge stock and the hydrogen through an ebullient bed of manganese nodule. The reaction may also be carried out by contacting the charge stock, the hydrogen, and manganese nodule in a batch reactor.

The demetalation may be carried out on any hydrocarbon charge stock containing organo-metallic compounds. Ordinarily, these will be hydrocarbon charge stocks containing sufficient metal to cause difficulty in the processing,'or other subsequent use, of the charge stocks. Other subsequent use of the charge stocks can include burning of the charge stock as fuel wherein the metals cause corrosion problems. These charge stocks include whole crude petroleum oils, topped crude oils, residual oils, distillate fractions, heavy vacuum gas oils, shale oils, oils from tar sands, and other heavy hydrocarbon oils. Charge stocks derived from Mid-Continent and East Texas crudes contain small amounts of metals. For example, some East Texas crudes contain about 0.1 part per million of vanadium and 24 parts per million of nickel. Charge stocks derived from West Texas crudes and foreign crudes, however, can contain larger amounts of metal. Kuwait crude can contain over 32 parts per million of vanadium and over 9 parts per million of nickel while Venezuelan crude can contain 200-400 parts per million of vanadium and 17-59 parts per million of nickel.

An advantage of the use of manganese nodules as a catalyst for demetalation resides in economy with respect to hydrogen consumption. During the demetalation reaction, hydrogen is consumed and the consumption of the hydrogen adds to the cost of demetalation. Thus, reduction in the consumption of the hydrogen is economically desirable. It has been suggested that the reduced hydrogen consumption to a large extent is due to the sensitivity of the manganese nodules to the effects of sulfur. Manganese nodules, as well as other catalysts heretofore employed for the demetalation of hydrocarbon charge stocks, effect hydrogenation of molecules other than those containing metals. Thus, the manganese nodules, as well as other demetalation catalysts, will effect hydrogenation of benzene rings, for example. This hydrogenation of molecules other than those containing metals therefore results in consumption of hydrogen in addition to that related to demetalation and, from the standpoint of the desired demetalation, represents a waste of hydrogen. However, as contrasted with other demetalation catalysts, the manganese nodules, in the presence of sulfur, have essentially no activity for hydrogenating benzene and other aromatic molecules. They will, however, hydrogenate olefins. Hydrocarbon charge stock contains sulfur to a greater or lesser extent, and, regardless of whether the manganese nodule is subjected to a sulfiding pretreatment, the sulfur in the hydrocarbon charge stock will effect a rapid sulfiding of the nodules. As a result, hydrogenation of the aromatic constituents of the charge stock is reduced with resulting reduction in the consumption of the hydrogen.

Whereas a rapid sulflding of the nodules will occur from the sulfur in the hydrocarbon charge stocks, sulflding pretreatment of the nodules, as previously described, is of value. It is believed that, under reducing conditions, a reduction of the metal oxides in the nodules can occur with consequent loss in surface area and diminished activity. The sulfides are, on the other hand, more stable to reduction. Thus, when the nodules are exposed to a reducing environment either before or during sulfiding as occurs when sulfiding results from the sulfur in the charge stock, a pre-reduction'or competitive reduction of the oxides can take place.

The following examples will be illustrative of the invention.

In each of these examples, manganese nodules recovered from the bottom of Sturgeon Bay in Lake Michigan were treated to remove at least a portion of the manganese dioxide component. Thereafter, the manganese nodules were treated by presulfiding with hydrogen sulflde. The nodules were then analyzed to determine their surface area, particle density, pore diameter, pore volume, and real density. The same analysis was made on the nodules prior to removal of at least a portion of their manganese dioxide component. Next, the manganese nodules were employed as a catalyst for demetalation of a hydrocarbon charge stock. The charge stock in each example was an Agha Jari petroleum crude oil which had been topped to remove all components boiling at temperatures below 400 F. The charge stock employed in Example 1 was different from the charge stock employed in Examples 2 and 3 with respect to the concentration of metals therein. Demetalation was carried out under the following conditions: temperature 750 F.; pressure 1,000 psig; liquid hourly space velocity 3.0; and hydrogen circulation rate 10,000 standard cubic feet per barrel of charge stock. Analyses of the charge stocks were made after the catalysts had been on stream for 3 hours and 50 hours in Examples 1 and 2 and after 1 hour and 48 hours in Example 3.

The analyses of the manganese nodules prior and subsequent to treatment to remove at least a portion of their manganese dioxide component are given in Table I.

Table II gives the results of the demetalation employing the catalysts of Examples 1 and 2. This table indicates the time on stream, the amount of nickel and vanadium, in parts per million (ppm), of the charge stock prior and subsequent to demetalation treatment for the two times on stream, the percent removal of nickel and vanadium, the total percent removal of metal, the percent of sulfur in the charge stock prior and subsequent to the demetalation treatment, and the percent of sulfur removed.

Table III gives the same information as Table l for Example 3.

EXAMPLE 1 The nodules, in the amount of 50 grams (g), were slowly heated to 800 F. in a stream of carbon monoxide. They were held at this temperature for 16 hours with the flow of carbon monoxide being maintained. The nodules were thereafter cooled. They had changed from brown to black in color and were now magnetic. The nodules were then added to a solution of 1 liter of 29 percent ammonium hydroxide, 288 g of ammonium carbonate, and 350 cubic centimeters (cc) of distilled water, and stirred at room temperature for 3 hours. The solution became quite black. The nodules were filtered, washed thoroughly with distilled water, and dried. Analysis for manganese indicated that approximately 30 percent of the manganese dioxide was removed by the procedure.

The nodules were then employed as catalyst for demetalation of the Agha Jari hydrocarbon charge stock.

It will be seen from the data in Table II that the treated nodules were superior to untreated nodules at both 3 hours and 50 hours on stream. It will also be seen from the table that the treated nodules were superior to untreated nodules for sulfur removal.

EXAMPLE 2 The nodules, in the amount of 50 g, were placed in a flask along with 19.4 g'of sodium chloride and 500 cc of IN acetic acid. The mixture was refluxed for 2 1% hours. As a result of the reaction in the flask, manganese dioxide was converted to manganous chloride and the manganous chloride was dissolved in the acetic acid solution and removed from the nodules. The equation for the reaction is:

MnO 4NaCl 4 HOOCCH MnCl Cl 4 NaOOCCH, 2 H O In this reaction, the acetic acid assisted in reaction of the sodium chloride with the manganese dioxide. Further, the acetic acid was of advantage because the resulting sodium acetate-acetic acid buffer kept the pH of the solution above 3, thus preventing solution of the iron. The nodules were filtered, washed thoroughly with distilled water, and dried. Analysis for manganese indicated that 35 percent of the manganese dioxide in the nodules was removed. The nodules were then employed for demetalation of hydrocarbon charge stock.

It will be seen from Table 11 that, although'the initial demetalation activity, i.e., after three hours on stream, is somewhat poorer than that of untreated nodules, the treated nodules were superior to untreated nodules after 50 hours on stream.

EXAMPLE 3 The nodules, ground to 14/30 mesh, were treated by passing 100 percent sulfur dioxide over them at l90-260 F. for 2 1% hours at a gas input rate of 780 volumes of gas per hour per volume of nodule. As a result of this treatment, manganese dioxide was converted to manganous sulfate. The nodules were then exhaustively extracted with boiling water in a Soxhlet apparatus. As a result, manganous sulfate was removed from the nodules. The catalyst was then dried at 230 F. The extract was evaporated to dryness in a rotary evaporator. The recovered solids, 5 percent based on the starting material, were analyzed by X-ray fluorescence and found to contain essentially only manganese salts.

The manganese nodules were then employed as catalysts for the demetalation of the hydrocarbon charge stock.

As shown in Table III, the performance of the treated nodules is superior to that of the untreated nodules at both 1 hour and 48 hours on stream.

S (112) 2.20 1.43 1.83 1.28 1.74 S removal (91:) 35 17 42 21 We claim:

I. A process for the demetalation of a hydrocarbon charge stock containing metals selected from the class consisting of whole crude petroleum oils, topped crude oils, residual oils, distillate fractions, heavy vacuum gas oils, shale oils, oils from tar sands, and heavy hydrocarbon oils, comprising removing from a manganese nodule containing manganese dioxide and iron oxide along with oxides of silicon and aluminum, carbonates of calcium and magnesium, the sulfate and phosphate of calcium and small amounts of the oxides of molybdenum, zinc, lead, vanadium, and rare earth metals at least a 25 percent by weight portion of said manganese dioxide component of said manganese nodule selectively with respect to said iron oxide component of said manganese nodule and thereafter contacting said hydrocarbon charge stock with hydrogen in the presence of said manganese nodule at a temperature from about 650 F. to about 850 F. and a pressure from about 100 to 3,000 pounds per square inch gage.

of said manganese nodule to a compound which is soluble in a solvent in which said iron oxide component of said manganese nodule or any derivative of said iron oxide component of said manganese nodule formed concomitantly with said compound is substantially insoluble and leaching said manganese nodule with said solvent to dissolve and remove said compound from TABLE 1 said manganese nodule. Untreated Nodules Ex. 1 EX. 2 EX 3 3. The process of claim 2 where n said portion of sa d S f Area manganese dioxide component is converted to said 12": 'SZhf 209 163 216 147 compound by contacting said manganese nodule with S1 g i 40 a reagent capable of reducing the manganese of said centimeter 1.4 1-72 L37 manganese dioxide component to the divalent state. Rig'figliih; g1 64 95 4. The process of claim 3 wherein said compound is Pore Volume dissolved and removed from said manganese nodule by g ig i per 041 026 044 leaching said manganese nodule with an aqueous sol- Real Density vent.

rams er cubic cemgnem 375 3.10 3:75 347 5. The process of claim 3 wherein said reagent is car .bsit qp ud TABLE II Charge Example 1, Example 2,

stock Untreated nodules treated nodules treated nodules Time on stream (hrs.) 3 3 50 3 S0 l7 4 14 5 l2 6 13 V (p.p.m.) 72 17 5O 13 45 20 46 Ni removal (percent)... 76 16 71 29 64 23 V removal (percent) 76 3O 82 37 72 36 Total metal removal (percent) 76 27 80 34 70 33 5 (percent) 2.01 1.63 1.89 1.35 1.75 1.51 1.81 S removal (percent) 19 6 33 13 25 10 TABLE 111 6. The process of claim 4 wherein said aqueous solvent is an alkaline aqueous solution. Example I v 3 7. The process of claim 3 wherein sa1d reagent is cargmf 5:33a Ezra bon monoxide and said alkaline aqueous solution is an Time on stream (hrs) 1 48 1 48 aqueous solutionof ammonium hydroxide and ammo- Ni( pm) 13.3 4.4 10.0 3.5 9.0 v (p pm) 45.8 9.0 22.5 3.0 16.5 carbmate Ni removal 669 243 8. The process of claim 3 wherein said reagent is sor o tgi sigii zinoval 803 50.9 dium chloride dissolved in an aqueous acid medium (96) 77.3 45.0 89.0509 having a pH greater than 3.

9. The process of claim 3 wherein said reagent is sulfur dioxide.

10. The process of claim 9 wherein said aqueous solvent is water.

11. The process of claim 3 wherein said reagent is sulfur dioxide and said aqueous solvent is water.

12. The process of claim 1 wherein the amount of iron oxide component of said manganese nodule removed concomitantly with said manganese dioxide component of said manganese nodule is not greater than 10 percent of the amount of said manganese dioxide removed from said manganese nodule.

13. A process for the demetalation of a hydrocarbon charge stock containing metals selected from the class consisting of whole crude petroleum oils, topped crude oils, residual oils, distillate fractions, heavy vacuum gas oils, shale oils, oils from tar sands, and heavy hydrocarbon oils, comprising contacting a manganese nodule containing manganese dioxide and iron oxide along with oxides of silicon and aluminum, carbonates of calcium and magnesium, the sulfate and phosphate of calcium and small amounts of the oxides of molybdenum, zinc, lead, vanadium, and rare earth metals with a reagent capable of reducing the manganese of the manganese dioxide component of said manganese nodule to the divalent state to convert at least a portion of said manganese dioxide component to a compound which is soluble in a solvent in which the iron oxide component of said manganese nodule or any derivative of said iron oxide component of said manganese nodule formed concomitantly with said compound is substantially insoluble and leaching said manganese nodule to dissolve and remove from said manganese nodule at least a portion of said compound, said portion of said manganese component converted to said compound and dissolved and removed from said manganese nodule being at least 25 percent by weight of said manganese dioxide component of said manganese nodule and the amount of iron oxide component of said manganese nodule removed concomitantly with said manganese dioxide component being not greater than 10 percent by weight of said manganese dioxide component, and thereafter contacting said hydrocarbon charge stock with hydrogen in the presence of said manganese nodule at a temperature from about 650 F. to about 850 F. and a pressure from about to 3,000 pounds per square inch gage.

14. The process of claim 2 wherein said manganese nodule subsequently to removal of said portion of said manganese dioxide component is subjected to the action of hydrogen sulfide by contacting said manganese nodule with said hydrogen sulfide.

15. The process of claim 13 wherein said manganese nodule subsequently to removal of said portion of said manganese dioxide component is subjected to the action of hydrogen sulfide by contacting said manganese nodule with said hydrogen sulfide. =1= 

2. The process of claim 1 wherein said 25 percent by weight portion of said manganese dioxide component of said manganese nodule is removed from said manganese nodule by converting at least a 25 percent by weight portion of said manganese dioxide component of said manganese nodule to a compound which is soluble in a solvent in which said iron oxide component of said manganese nodule or any derivative of said iron oxide component of said manganese nodule formed concomitantly with said compound is substantially insoluble and leaching said manganese nodule with said solvent to dissolve and remove said compound from said manganese nodule.
 3. The process of claim 2 wherein said portion of said manganese dioxide component is converted to said compound by contacting said manganese nodule with a reagent capable of reducing the manganese of said manganese dioxide component to the divalent state.
 4. The process of claim 3 wherein said compound is dissolved and removed from said manganese nodule by leaching said manganese nodule with an aqueous solvent.
 5. The process of claim 3 wherein said reagent is carbon monoxide.
 6. The process of claim 4 wherein said aqueous solvent is an alkaline aqueous solution.
 7. The process of claim 3 wherein said reagent is carbon monoxide and said alkaline aqueous solution is an aqueous solution of ammonium hydroxide and ammonium carbonate.
 8. The process of claim 3 wherein said reagent is sodium chloride dissolved in an aqueous acid medium having a pH greater than
 3. 9. The process of claim 3 wherein said reagent is sulfur dioxide.
 10. The process of claim 9 wherein said aqueous solvent is water.
 11. The process of claim 3 wherein said reagent is sulfur dioxide and said aqueous solvent is water.
 12. The process of claim 1 wherein the amount of iron oxide component of said manganese nodule removed concomitantly with said manganese dioxide component of said manganese nodule is not greater than 10 percent of the amount of said manganese dioxide removed from said manganese nodule.
 13. A process for the demetalation of a hydrocarbon charge stock containing metals selected from the class consisting of whole crude petroleum oils, topped crude oils, residual oils, distillate fractions, heavy vacuum gas oils, shale oils, oils from tar sands, and heavy hydrocarbon oils, comprising contacting a manganese nodule containing manganese dioxide and iron oxide along with oxides of silicon and aluminum, carbonates of calcium and magnesium, the sulfate and phosphate of calcium and small amounts of the oxides of molybdenum, zinc, lead, vanadium, and rare earth metals with a reagent capable of reducing the manganese of the manganese dioxide component of said manganese nodule to the divalent state to convert at least a portion of said manganese dioxide component to a compound which is soluble in a solvent in which the iron oxide component of said manganese nodule or any derivative of said iron oxide component of said manganese nodule formed concomitantly wiTh said compound is substantially insoluble and leaching said manganese nodule to dissolve and remove from said manganese nodule at least a portion of said compound, said portion of said manganese component converted to said compound and dissolved and removed from said manganese nodule being at least 25 percent by weight of said manganese dioxide component of said manganese nodule and the amount of iron oxide component of said manganese nodule removed concomitantly with said manganese dioxide component being not greater than 10 percent by weight of said manganese dioxide component, and thereafter contacting said hydrocarbon charge stock with hydrogen in the presence of said manganese nodule at a temperature from about 650* F. to about 850* F. and a pressure from about 100 to 3,000 pounds per square inch gage.
 14. The process of claim 2 wherein said manganese nodule subsequently to removal of said portion of said manganese dioxide component is subjected to the action of hydrogen sulfide by contacting said manganese nodule with said hydrogen sulfide.
 15. The process of claim 13 wherein said manganese nodule subsequently to removal of said portion of said manganese dioxide component is subjected to the action of hydrogen sulfide by contacting said manganese nodule with said hydrogen sulfide. 